JP6931270B2 - A gas-liquid reaction device equipped with a micro-nano bubble generator and a gas-liquid reaction method using this gas-liquid reaction device. - Google Patents

Description

The present invention relates to a gas-liquid reactor in which a liquid containing a reactant and a gas containing a reaction gas are reacted in a reaction vessel, and a gas-liquid reaction method using the gas-liquid reactor.

A liquid containing a reactant (hereinafter, also referred to as “reactant-containing liquid”) and a gas containing a reaction gas (hereinafter, also referred to as “reactive gas”) are mixed to carry out a gas-liquid reaction with high efficiency. In order to do this, it is important to increase the contact area between the two.

In order to satisfy this requirement, as described in Patent Document 1, a liquid containing a reactant and a reaction gas are put into a reaction vessel and heated in a closed manner, and the contact area between the two is increased by stirring to carry out a gas-liquid reaction. A batch or continuous process method in which a large number of disks are attached close to the axis of rotation are rotated in a state where they are partially infiltrated into the liquid containing the reactants, and gas is applied to the thin film of the solution formed on the surface of the disks. A disk method for causing a reaction gas, a jet method for causing a contact reaction by ejecting a jet stream of a reactant-containing liquid into a reaction gas, and the like are adopted.

The above-mentioned batch method or continuous process method is advantageous as a method for carrying out a gas-liquid reaction in a large amount and efficiently on an industrial scale, but in order to increase the efficiency of the gas-liquid reaction, a liquid phase is used in a reaction gas atmosphere. It is necessary to vigorously stir in order to increase the contact area between the gas phase and the gas phase. Further, in order to increase the efficiency of the gas-liquid reaction, it is necessary to carry out the gas-liquid reaction under high temperature and high pressure.
As a technique for efficiently performing a gas-liquid reaction, as shown in FIG. 7, Patent Document 2 describes this in a gas-liquid reaction in which benzene is converted to cyclohexane from a reactor 110 containing a liquid containing benzene by a pump 105. A gas-liquid reactor is disclosed in which a liquid is extracted and supplied to a high shearing apparatus 140, and the liquid is contained with hydrogen gas bubbles having an average bubble diameter of 100 μm and returned to the reactor 110. Further, in Patent Document 3, as shown in FIG. 8, in a gas-liquid reaction for converting an aromatic nitro compound into an aromatic amine compound, an aromatic nitro compound solution 208 is extracted from a vial bottle 209 through a filter 207 to release hydrogen gas. Disclosed is a gas-liquid reactor that is introduced to contain hydrogen microbubbles, introduced into a catalyst fixator to allow the hydrogenation reaction to proceed, and then refluxed into a vial 209.

However, in a gas-liquid reactor as in Patent Document 2, in order to carry out a gas-liquid reaction with high efficiency, it is necessary to set the pressure in the reactor 110 to a high pressure of usually 5 MPa to 20 MPa, but a high shearing apparatus. It is difficult to maintain and operate the circulation path of the liquid containing benzene containing 140 at such a high pressure, and it is difficult to install, operate, and maintain the device economically and efficiently.

Further, in a gas-liquid reactor as in Patent Document 3, it is difficult to process a large amount of an aromatic nitro compound solution 208 containing hydrogen microbubbles through a catalyst fixator, so that it is difficult to process the gas-liquid reaction. Since it is difficult to carry out a liquid reaction under high temperature and high pressure, it is not suitable as a device for performing a large amount and efficient gas-liquid reaction on an industrial scale.

The present inventors can carry out a gas-liquid reaction in a large amount and efficiently on an industrial scale, and can economically and efficiently install, operate, and maintain the device, and a gas-liquid reaction device and this gas. The present invention has been made by diligently researching a gas-liquid reaction method using a liquid reactor.

International Publication No. 2007/100052 Special Table 2010-531882 Japanese Unexamined Patent Publication No. 2014-005217

The problem of the gas-liquid reaction device of the present invention and the gas-liquid reaction method using this gas-liquid reaction device is that a large amount of gas-liquid reaction can be efficiently performed on an industrial scale, and the device is installed, operated, and maintained. It is an object of the present invention to provide a gas-liquid reaction apparatus capable of economically and efficiently performing the above, and a gas-liquid reaction method using the gas-liquid reactor.

In order to solve the above problems, in the gas-liquid reactor of the present invention and the gas-liquid reaction method using the gas-liquid reactor, a micro-nano bubble generator is provided in the reaction vessel of the gas-liquid reactor, and the micro-nano bubbles are provided. The reactant-containing liquid existing in the liquid phase of the reaction tank and the reaction gas existing in the gas phase of the reaction tank are supplied to the generator, and the reactant-containing liquid containing micro-nanobubbles of the reaction gas is supplied to the liquid phase. It is characterized by that.

Further, as the micro-nano bubble generator, a liquid flow type device capable of economically generating a large amount of micro-nano bubbles, which is outlined in FIG. 6 and described later, is used, and this micro-nano bubble generator is used. To further solve the above problems, the reactant-containing liquid existing in the liquid phase of the reaction tank is pressurized and supplied, and the reaction gas is sucked from the gas phase of the reaction tank by the negative pressure generated thereby. Can be done.

The gas-liquid reaction device of the present invention and the gas-liquid reaction method using this gas-liquid reaction device have the following excellent effects.

By adopting the gas-liquid reaction of the batch type or continuous process method and performing the gas-liquid reaction at high temperature and high pressure in an airtightly sealed reaction tank, the gas-liquid reaction can be carried out in large quantities and efficiently on an industrial scale. It can be carried out.

Further, by incorporating micro-nano bubbles of the reaction gas into the reactant-containing liquid using a micro-nano bubble generator, the contact area between the liquid phase and the gas phase can be increased without vigorous stirring, and the gas-liquid reaction can be made efficient. Can be done economically and economically.

Further, by supplying the reactant-containing liquid containing the micro-nano bubbles of the reaction gas to the liquid phase from the micro-nano bubble generator, the liquid phase can be agitated, and the gas-liquid reaction can be efficiently and economically performed. be able to.

Further, by providing the micro-nano bubble generator in the reaction vessel, the inside of the reaction vessel can be stably maintained at a high pressure, and the apparatus can be installed, operated and maintained economically and efficiently. Furthermore, a liquid flow type is used as the micro-nano bubble generator, and the reactant-containing liquid existing in the liquid phase of the reaction tank is pressurized and supplied to this micro-nano bubble generator, and the negative pressure generated by this pressurizes and supplies the air in the reaction tank. By sucking the reaction gas from the phase and supplying the reactant-containing liquid containing the micro-nanobubbles of the reaction gas to the liquid phase, the reactant-containing liquid in the liquid phase can be agitated more efficiently and economically.

Further, by using such a micro-nano bubble generator, the average diameter of the number of micro-nano bubbles and the total number of bubbles can be determined not only by the pressure and flow rate of the reactant-containing liquid supplied to the micro-nano bubble generator, but also by the gas in the reaction tank. It can also be adjusted by the pressure of the reactive gas present in the phase.

It is a schematic diagram which shows the 1st Embodiment of the gas-liquid reaction apparatus of this invention. It is a schematic diagram which shows the 2nd Embodiment of the gas-liquid reaction apparatus of this invention. It is a schematic diagram which shows the 3rd Embodiment of the gas-liquid reaction apparatus of this invention. It is a schematic diagram which shows the 4th Embodiment of the gas-liquid reaction apparatus of this invention. It is a schematic diagram which shows the 5th Embodiment of the gas-liquid reaction apparatus of this invention. It is sectional drawing which shows the outline of the micro-nano bubble generator which can be suitably used in the gas-liquid reaction apparatus of this invention. FIG. 1 is a conventional example of Patent Document 2 (Japanese Patent Publication No. 2010-531882). FIG. 1 is a conventional example of Patent Document 3 (Japanese Unexamined Patent Publication No. 2014-005217).

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, but the present invention is not limited thereto. In the following description, a gas-liquid reaction in which a hydrogenation reaction of an organic compound is carried out, which is a typical example of a reduction reaction, will be mainly described, but the gas-liquid reaction apparatus of the present invention and a gas-liquid reaction method using this gas-liquid reaction apparatus will be described. Can of course be used in gas-liquid reactions using organic or inorganic chemical substances such as these fats and oils, fatty acids, and synthetic resins.

1. 1. General Matters of the Present Invention First, regarding the general matters of the gas-liquid reactor of the present invention and the gas-liquid reaction method using the gas-liquid reactor (hereinafter, also referred to as "the device and method of the present invention"). explain.

The apparatus and method of the present invention is a gas-liquid reaction of a batch type or continuous process method, in which a liquid containing a reactant (liquid containing a reactant) and a pressurized reaction are placed in a tightly sealed reaction vessel. A gas containing a gas (reaction gas) is supplied to form a liquid phase and a gas phase, and a gas-liquid reaction is carried out. Further, in order to improve the reaction efficiency of the gas-liquid reaction, it is preferable to carry out the gas-liquid reaction at a high temperature and a high pressure.

〇 Gas-liquid reaction The gas-liquid reaction to which the apparatus and method of the present invention can be applied is not particularly limited, and can be applied to a known gas-liquid reaction usually carried out under high temperature or high temperature / high pressure.
For example, radical carbonylation reaction, hydroformation reaction of olefin, direct hydrogenation reaction, oxygen oxidation reaction (reaction to obtain aldehyde from alcohol, reaction to obtain epoxy from alkene, photomonomorphic oxygen oxidation reaction, α-position oxidation reaction of ester, etc. ), Hydrogenation reaction (production of sugar alcohol by hydrogenation of reduced sugar, hydrogenation reaction of olefin, hydrogenation reaction of carbonyl compound, hydrogenation reaction of cyano group, production of hardened oil by hydrogenation of unsaturated glyceride of natural fats and oils , Reaction of hydrogenating unsaturated fatty acids with a nickel catalyst, etc.), photohalogenation reaction of alkenes, Heck carbonylation reaction.

〇 Liquid containing reactant (liquid containing reactant)
The reactant-containing liquid used in the apparatus and method of the present invention may contain only the reactant or may contain the reactant and the solvent.

As the solvent, one or more kinds such as water, an organic solvent, an ionic liquid (also referred to as an ionic liquid, an ionic fluid, and a room temperature molten salt), and a liquid inorganic compound can be used. Examples of the organic solvent include aliphatic hydrocarbons such as hexane, aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, diethyl ketone and methyl ethyl ketone, aldehydes such as butyl aldehyde, diethyl ether and dibutyl ether. Ethers such as diisobutyl ether, tetrahydrofuran and dioxane, esters such as ethyl acetate, butyl acetate and di-n-octylphthalate, amines such as triethylamine, pyrrolidine and piperidine, amides such as dimethylformamide, and sulfoxides such as dimethylsulfoxide. Classes, alcohols such as methanol, ethanol, propanol and isopropanol, diols such as ethylene glycol, propanediol and butanediol, nitriles such as acetonitrile, heteroaromatic compounds such as pyridine, carbon tetrachloride, chloroform, dichloromethane and dichloroethan. Examples thereof include halogen solvents such as halogen solvents such as, carboxylic acids such as acetic acid and formic acid, sulfonic acids, and fluorine-based inert liquids such as Florinate (registered trademark), and a mixed solvent of any ratio of two or more of these can also be used. Examples of the liquid inorganic compound include phosphoric acids such as sulfuric acid, phosphoric acid and phosphorous acid, nitric acid, hydrogen peroxide solution and the like. As the solvent, among them, an aqueous solvent and an organic solvent are preferable, aromatic hydrocarbons, hydrocarbons and alcohols are more preferable, and aromatic hydrocarbons are particularly preferable.

When a solvent is used, the amount used is not limited, and the concentration of the reactant used is usually 0.001 mol or more, preferably 0.02 mol or more, and more preferably 0.1 mol or more with respect to 1 liter of the solvent. Therefore, it is preferable to use an amount of the solvent such that the amount is 20 mol or less, preferably 10 mol or less, and more preferably 5 mol or less. If the amount of the solvent is larger than the above range, the productivity is lowered, and if the amount of the solvent is smaller than the above range, the catalyst or the reactant is dissolved, which is disadvantageous.

〇 Gas containing reactive gas (reactive gas)
Examples of the reaction gas include ozone, hydrogen, helium, fluorine, chlorine, carbon monoxide, carbon dioxide, sulfur dioxide, hydrogen chloride gas, ammonia gas, methane, ethane, propane, ethylene gas, acetylene gas and the like. Singlet oxygen and triplet oxygen can be mentioned. Further, a mixed gas of these or a mixed gas of these reaction gases and another gas may be used.

The concentration of the reactive gas in the gas component is not particularly limited, but is selected from the range of 0.01 to 100% by volume, preferably 0.1% or more, more preferably 5% or more, and particularly preferably. Is 10% or more. If the concentration of the reaction gas is lower than the above range, it will be difficult to obtain sufficient reaction efficiency.

〇Catalyst In the apparatus and method of the present invention, a catalyst may or may not be used for the gas-liquid reaction, but usually, the gas-liquid reaction can be performed more efficiently by using the catalyst. preferable.

As the catalyst, those containing at least one of the elements (metals) of Groups 4 to 12 of the Periodic Table and the elements (metals) selected from the lanthanoids can be preferably used, and the catalysts are silica, alumina, and the like. It can be used by supporting it on the surface of a porous material such as silica-alumina, zeolite, or activated carbon. For example, when a hydrogenation reaction of a reducing sugar is carried out, a Raney nickel catalyst or the like can be used.

When a catalyst is used, a homogeneous catalyst is preferably used by being contained in a reactant-containing liquid present in the liquid phase in the reaction vessel. The amount of the catalyst used is not particularly limited, but is preferably 0.1 ppm or more, particularly 1 ppm or more, 10% or less, and particularly 1% or less as the amount of the active ingredient with respect to the reactant.

〇 Reaction conditions As described above, the apparatus and method of the present invention employ a gas-liquid reaction of batch or continuous process methods, and gas-liquid reactions are usually performed at high temperature and high pressure in an airtightly sealed reaction vessel. Although the reaction is carried out, the optimum range of conditions such as the temperature in the reaction vessel, the pressure in the reaction vessel, and the reaction time is appropriately set according to the gas-liquid reaction, the reactant, the type of reaction gas, etc. can do.

For example, when the hydrogenation reaction of a reducing sugar is carried out, the lower limit of the temperature in the reaction vessel is preferably 20 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 80 ° C. or higher, and particularly preferably 110 ° C. or higher. The upper limit is preferably 350 ° C. or lower, more preferably 300 ° C. or lower, further preferably 250 ° C. or lower, particularly preferably 200 ° C. or lower, and the lower limit of hydrogen pressure is preferably 0.1 MPa or higher, more preferably 0.5 MPa or lower. The above is more preferably 1 MPa or more, particularly preferably 5 MPa or more, the upper limit is preferably 30 MPa or less, more preferably 25 MPa or less, still more preferably 20 MPa or less, and the reaction time is preferably 30 minutes or more and 9 hours or less.

2. The first feature of the present invention The apparatus and method of the present invention carry out the gas-liquid reaction of the batch type or continuous process method as described above, and in this reaction, the micro-nano bubble generator provided in the reaction vessel is used. The first feature is that the reactant-containing liquid existing in the liquid phase of the reaction tank contains micro-nano bubbles of the reaction gas existing in the gas phase of the reaction tank and is supplied to the liquid phase.

In this way, the gas-liquid reaction of the batch type or continuous process method is adopted, and the gas-liquid reaction is carried out under high pressure, preferably at high temperature and high pressure in an airtightly sealed reaction tank. It can be done in large quantities and efficiently on an industrial scale.

Further, by incorporating micro-nano bubbles of the reaction gas into the reactant-containing liquid using a micro-nano bubble generator, the contact area between the liquid phase and the gas phase can be increased without vigorous stirring, and the gas-liquid reaction can be made efficient. Can be done economically and economically.

Further, by supplying the reactant-containing liquid containing micro-nano bubbles of the reaction gas from the micro-nano bubble generator to the liquid phase, the liquid phase can be appropriately agitated without installing a culture tank stirrer. It is possible to carry out gas-liquid reaction efficiently and economically.

Further, by providing the micro-nano bubble generator inside the reaction vessel, the inside of the reaction vessel can be stably maintained at a high pressure as compared with the case where the micro-nano bubble generator is provided outside the reaction vessel, and the installation, operation and maintenance of the apparatus can be performed. It can be done economically and efficiently.

〇 Micro-nano bubbles of reactive gas In the present invention, micro-nano bubbles of reactive gas are contained in the reactant-containing liquid, and the “micro-nano bubbles” of the present invention mean “micro-bubbles” and / or “nano-bubbles”. While "ordinary bubbles" rapidly rise in water and burst at the surface and disappear, microbubbles with a diameter of 50 μm or less, called "microbubbles," shrink and disappear in water. Along with free radicals, "nano bubbles", which are microbubbles having a diameter of 100 nm or less, are generated, and these "nano bubbles" remain in water for a certain period of time.

In the present invention, bubbles having a number average diameter of 100 μm or less are referred to as “micro bubbles”, and bubbles having a number average diameter of 1 μm or less are referred to as “nano bubbles”. As a method for measuring bubbles such as micro-nano bubbles and nano bubbles, an electric detection band method, a resonance type mass measurement method, a particle trajectory analysis method, and the like are generally used.

"Nano bubbles", which are micro bubbles, are also called "ultra fine bubbles". At present, ISO (International Organization for Standardization) is considering the creation of an international standard for fine bubble technology, and if an international standard is created, the name "nano bubble" that is generally used at present will be used. There is a possibility that it will be unified into "ultra fine bubble".

Number of micro-nano bubbles If the average diameter is too large, the micro-nano bubbles will expand due to the pressure drop in the micro-nano bubbles as the micro-nano bubbles rise in the liquid phase, resulting in the specific surface area of the micro-nano bubbles (surface area per unit weight). ) Decreases the effect of promoting the gas-liquid reaction.

Further, in order to increase the specific surface area of the micro-nano bubbles, the number of micro-nano bubbles per unit volume in the reactant-containing liquid to be brought into contact with the reactant (hereinafter referred to as "total number of bubbles") is also important. Reactant total bubble per-containing liquid 1mL 10 ⁵ or more, preferably ¹⁰ 6 to 10 ^9, more preferably be generated so that ^from 107 ^{to 1010} pieces.

Optimal ranges can be appropriately set for the average diameter of the number of these micro-nano bubbles and the total number of bubbles according to the gas-liquid reaction, the reactant, the type of reaction gas, etc., and the structure of the micro-nano bubble generator described later. , Can be adjusted and set according to the generation conditions.

By including micro-nanobubbles of the reaction gas in the reactant-containing liquid, the reaction gas can remain in the reactant-containing liquid for a long period of time, and the restriction of mass transfer in the gas-liquid reaction can be reduced. A small number average diameter of micro-nano bubbles does not adversely affect the reaction rate, but it is economical if the average number of micro-nano bubbles is too small because the saturation of the reactant-containing liquid in the reaction gas is limited. Will be inefficient. Further, the total number of bubbles can be generated under the setting conditions of the micro-nano bubble generator, and it is preferable that the number of micro-banano bubbles can be stably present in the reaction with the reactant.

〇 Micro-nano bubble generator As the micro-nano bubble generator, a known or commercially available device can be used. For example, a sufficient amount of gas is dissolved in water at a certain high pressure and then the pressure is released. A "pressurized dissolution type micro-nano bubble generator" that creates hypersaturation conditions for the gas dissolved in It is possible to use a "loop flow type bubble generation nozzle" or the like that utilizes the phenomenon that the bubbles are subdivided by the gas.

3. 3. The second feature of the present invention The apparatus and method of the present invention use a liquid flow type as a micro-nano bubble generator provided in the reaction vessel, and the micro-nano bubble generator contains a reactant existing in the liquid phase of the reaction vessel. The second feature is that the liquid is pressurized and supplied, the reaction gas is sucked from the gas phase of the reaction tank by the negative pressure generated by this, and the reactant-containing liquid containing micro-nano bubbles of the reaction gas is supplied to the liquid phase. Is to be.

By using such a micro-nano bubble generator, it is possible to efficiently and economically supply the reactant-containing liquid containing the micro-nano bubbles of the reaction gas to the liquid phase, and the liquid phase of the reactant-containing liquid can be supplied. Can be agitated more efficiently and economically.

Further, the average diameter of the number of micro-nano bubbles and the total number of bubbles are adjusted not only by the pressure and flow rate of the reactant-containing liquid supplied to the micro-nano bubble generator, but also by the pressure of the reaction gas existing in the gas phase of the reaction vessel. be able to.

This liquid flow type micro-nano bubble generator will be described with reference to FIG.
As the micro-nano bubble generator 4, a liquid flow method, that is, a method of generating micro-nano bubbles by a liquid flow can be used, and a typical one of this liquid flow type micro-nano bubble generator is a nozzle type. Micro-nano bubble generator can be mentioned. This nozzle-type micro-nano bubble generator is as shown in FIG.

In FIG. 6, the reactant-containing liquid E (hereinafter, also referred to as “liquid E”) existing in the liquid phase of the reaction tank is pressurized and supplied from the inlet portion 11 of the nozzle, and is supplied from the inlet portion 11 of the nozzle as the diameter of the pipe is reduced. The flow velocity is increased to generate turbulence in the throat portion 12. The reaction gas F present in the gas phase of the reaction vessel is sucked from the gas inlet 14 by the negative pressure generated by the flow of the liquid E, mixed with the liquid E at the suction section 13, and micro-nano bubbles due to the turbulent flow at the throat section 12. Will be. The reactant-containing liquid G containing micro-nano bubbles of the reaction gas thus formed is supplied to the liquid phase from the outlet portion 15.

4. Embodiment of the present invention Next, using FIGS. 1 to 5, the first embodiment (FIG. 1), the second embodiment (FIG. 2), the third embodiment (FIG. 3), and the fourth embodiment of the present invention are used. FIG. 4 and a fifth embodiment (FIG. 5) will be described.

In the first to fifth embodiments, a nozzle type micro-nano bubble generator 4 is used, but in the first and fifth embodiments, the micro-nano bubble generator 4 is the gas phase of the reaction vessel 1. It is provided in D, is provided in the liquid phase C of the reaction tank 1 in the second embodiment, and straddles the gas phase D and the liquid phase C of the reaction tank 1 in the third embodiment and the fourth embodiment. Is provided. When the micro-nano bubble generator 4 is provided in the gas phase D of the reaction tank 1 as in the first embodiment and the fifth embodiment, the micro-nano bubbles of the reaction gas B are contained at the outlet of the micro-nano bubble generator 4. A pipe 8 is provided to guide and supply the reactant-containing liquid A into the liquid phase C.

Further, in the fourth embodiment, as a pump for supplying the reactant-containing liquid E existing in the liquid phase C of the reaction tank 1 to the micro-nano bubble generator 4, as in the other embodiments, the outside of the reaction tank 1 is used. An internal pump 6 in which a pump impeller (pump impeller) is arranged inside the reaction tank 1 is used instead of the pump 5 provided in the reaction tank 1. I am using it. In the fourth embodiment, the micro-nano bubble generator 4 is provided across the gas phase D and the liquid phase C of the reaction tank 1, but of course, as in the first embodiment and the fifth embodiment, the reaction tank is provided. It can be provided in the gas phase D of 1, or can be provided in the liquid phase C of the reaction vessel 1 as in the second embodiment.

Further, in the fifth embodiment, the gas-liquid reactor of the first embodiment is provided with a reaction tank stirrer 7 for stirring the reactant-containing liquid A of the liquid phase C.

First, the first embodiment of the present invention will be described with reference to FIG.
In the first embodiment, a gas-liquid reaction is carried out between a liquid containing a reactant (reactant-containing liquid) A and a gas containing a reaction gas (reactive gas) B as follows.
1) The liquid supply device 2 supplies the liquid containing the reactant (reactant-containing liquid) A to the airtightly sealed reaction tank 1, and the pressurized gas supply device 3 supplies the pressurized reaction gas. The contained gas (reaction gas) B is supplied to form the liquid phase C and the gas phase D of the reaction tank.
2) The temperature in the reaction vessel is raised to a predetermined temperature by a heating means (not shown) such as a heater, and the pressure in the reaction vessel is raised to a predetermined pressure by the pressurized gas supply device 3 to react. The gas-liquid reaction is started by setting the inside of the tank to a high temperature and high pressure state.
3) The reactant-containing liquid A is extracted from the liquid phase C of the reaction tank 1 by the pump 5 and pressurized.
It is supplied to the nozzle-type micro-nano bubble generator 4 provided in the gas phase D of the reaction tank 1.
4) Due to the negative pressure generated by the flow of the reactant-containing liquid A, the reaction gas A is sucked into the micro-nano bubble generator 4 from the gas phase D of the reaction vessel 1.
5) In this way, the reactant-containing liquid A containing the micro-nano bubbles of the reaction gas B is guided and supplied into the liquid phase C through the pipe 8 provided at the outlet of the micro-nano bubble generator 4. ..

In the first embodiment, the gas-liquid reaction of the batch process method is adopted, and the gas-liquid reaction is carried out under high temperature and high pressure in the airtightly sealed reaction tank 1, so that the gas-liquid reaction is carried out in large quantities on an industrial scale. And it can be done efficiently.

Further, by using the micro-nano bubble generator 4 to contain the micro-bananoble of the reaction gas B in the reactant-containing liquid A, the contact area between the liquid phase C and the gas phase D can be increased without vigorous stirring. , Gas-liquid reaction can be performed efficiently and economically.

Further, by guiding and supplying the reactant-containing liquid A containing the micro-nano bubbles of the reaction gas B into the liquid phase C from the micro-nano bubble generator 4, the liquid phase C can be agitated and the gas-liquid reaction can be performed. Can be done efficiently and economically.
Further, by providing the micro-nano bubble generator 4 in the reaction vessel 1, the inside of the reaction vessel 1 can be stably maintained at a high pressure, and the apparatus can be installed, operated and maintained economically and efficiently. Can be done.

Further, a liquid flow type is used as the micro-nano bubble generator 4, and the reactant-containing liquid A existing in the liquid phase C of the reaction tank 1 is pressurized and supplied to the micro-nano bubble generator, and the negative pressure generated thereby causes the micro-nano bubble generator 4. The reaction substance B is sucked from the gas phase D of the reaction tank 1, and the reactant-containing liquid A containing the micro-nanobubbles of the reaction gas B is guided into the liquid phase C and supplied to contain the reactant of the liquid phase C. The liquid A can be agitated more efficiently and economically.
Further, by using such a micro-nano bubble generator 4, the number average diameter of the micro-nano bubbles and the total number of bubbles can be adjusted not only by the pressure and flow rate of the reactant-containing liquid A supplied to the micro-nano bubble generator 4, but also by the reaction. It can also be adjusted by the pressure of the reaction gas B present in the gas phase D of the tank 1.

In particular, as in the first embodiment, the reactant-containing liquid A is extracted from the lower part in the vertical direction of the reaction tank 1, and the micro-nano bubbles of the reaction gas B are generated from the micro-nano bubble generator 4 provided in the upper part in the vertical direction of the reaction tank 1. By guiding and supplying the contained reactant-containing liquid A into the liquid phase C, the reactant-containing liquid A in the liquid phase C can be sufficiently stirred in the vertical and vertical directions.

The reaction tank 1 for performing the gas-liquid reaction is usually provided with a reaction tank stirrer 7 as in the fifth embodiment of the present invention shown in FIG. 5 in order to stir the reactant-containing liquid A in the liquid phase C. However, in the first embodiment, since the reactant-containing liquid A in the liquid phase C can be agitated by the circulation of the reactant-containing liquid A, it is not necessary to install the reaction tank stirrer 7, or even if it is installed. Since the energy required to drive the reaction tank stirrer 7 can be reduced, the installation, operation, and maintenance of the apparatus can be performed economically and efficiently.

Since the stirring condition of the reactant-containing liquid A in the liquid phase C differs depending on the volume of the reaction tank 1, the shape of the reaction tank 1, the depth of the liquid phase C, and the like, the stirring of the reactant-containing liquid A in the liquid phase C It is possible to adjust and design the installation position, inclination, number of installations, etc. of the micro-nano bubble generator 4 in the vertical and vertical directions in order to perform the above.

The vertical and vertical installation positions of the micro-nano bubble generator 4 can be provided in the gas phase D of the reaction vessel 1 as in the first and fifth embodiments, or as in the second embodiment. It can be provided in the liquid phase C of the reaction tank 1, or can be provided across the gas phase D and the liquid phase C of the reaction tank 1 as in the third and fourth embodiments.

Regarding the inclination of the micro-nano bubble generator 4, for example, the inclination of the micro-nano bubble generator 4 is such that the reactant-containing liquid A containing the microbubbles of the reaction gas B is supplied in the vertical downward direction of the reaction tank 1. If it is set as such, stirring can be performed mainly so as to convection in the vertical direction, and the reactant-containing liquid A containing the micro-nano bubbles of the reaction gas B is supplied in the tangential direction of the side wall of the reaction tank 1. If it is set as such, stirring can be performed so as to descend in a spiral shape.

Regarding the number of micro-nano bubble generators 4 installed in the vertical and vertical directions, for example, if a plurality of micro-nano bubble generators 4 are installed at equal intervals along the side wall of the reaction vessel 1, the liquid phase C can be installed. The reactant-containing liquid A can be uniformly stirred.

As the gas-liquid reaction progresses, the pressure of the gas phase D in the reaction tank 1 decreases. Therefore, in order to keep the pressure of the gas phase D constant and to carry out the gas-liquid reaction uniformly and uniformly, the reaction tank 1 It is preferable to provide a supply control device that measures the pressure of the gas phase D with a sensor and controls the supply amount of the reaction gas B from the pressurized gas supply device 3 based on the measured value.

Further, in the first embodiment, the gas-liquid reactor of the batch process method is shown, but the liquid of the liquid phase C of the reaction tank 1 is discharged while keeping the reaction tank 1 in an airtightly sealed state. By providing the device, a gas-liquid reaction device of a continuous process method can also be used. In this case, the liquid in the liquid phase C of the reaction tank 1 containing the reactant of the reactant and the reaction gas is continuously discharged by the discharge device from the liquid supply device 2 and the pressurized gas supply device 3. , A liquid containing a reactant (reactant-containing liquid) A and a gas containing a pressurized reaction gas (reactant gas) B, respectively, are continuously supplied.

In order to keep the liquid level of the liquid phase C of the reaction tank 1 constant and to carry out the gas-liquid reaction uniformly and uniformly, the discharge device is equipped with a liquid supply device according to the liquid level of the liquid phase C of the reaction tank 1. It is preferable to provide an discharge control device that controls the supply amount of the reactant-containing liquid A from 2 and / or the discharge amount of the liquid in the liquid phase C of the reaction tank 1.

Further, as means for pressurizing and supplying the reactant-containing liquid E existing in the liquid phase C of the reaction tank 1 to the micro-nano bubble generator 4, the first to third embodiments, the fifth embodiment A pump 5 provided outside the reaction tank 1 may be used as described above, or an internal pump 6 having a pump impeller (pump impeller) inside the reaction tank 1 may be used as in the fourth embodiment. You may. The internal pump 6 generally includes a pump shaft having a pump impeller fixed to one end and an electric motor connected to the pump shaft and driven to rotate, but all of these pump impellers, pump shafts and electric motors. Can be arranged inside the reaction tank 1, a pump shaft is provided so as to penetrate the wall of the reaction tank 1, a pump impeller is arranged inside the reaction tank 1, and an electric motor is arranged outside the reaction tank 1. You can also do it. Further, the pump impeller provided inside the reaction tank 1 is connected to the pump impeller such as a pump shaft to rotate and drive, and electromagnetic force, magnetic force, etc. are applied from the outside of the reaction tank 1 to the pump impeller. Can also be driven by rotation directly.

As described above, the gas-liquid reaction device of the present invention and the gas-liquid reaction method using the gas-liquid reaction device have the following excellent effects by having the above-mentioned first feature.
〇 By adopting a gas-liquid reaction of a batch type or continuous process method and performing a gas-liquid reaction at high temperature and high pressure in an airtightly sealed reaction tank, the gas-liquid reaction can be carried out in large quantities and efficiently on an industrial scale. Can be done.
〇 By containing micro-nano bubbles of reactive gas in the reactant-containing liquid using a micro-nano bubble generator, the contact area between the liquid phase and the gas phase can be increased without vigorous stirring, and the gas-liquid reaction is efficient.・ Can be done economically.
〇 By supplying a reactant-containing liquid containing micro-nano bubbles of the reaction gas to the liquid phase from the micro-nano bubble generator, the liquid phase can be agitated and the gas-liquid reaction can be carried out efficiently and economically. Can be done.
〇 By installing the micro-nano bubble generator in the reaction vessel, the inside of the reaction vessel can be stably maintained at a high pressure, and the equipment can be installed, operated, and maintained economically and efficiently. (Specifically, since the pressure difference between the inside and outside of the micro-nano bubble generator can be reduced, the wall thickness of the micro-nano bubble generator can be reduced, and the existing micro-nano bubble generator can be used without changing to a pressure resistant structure. There are merits. In addition, since the types and numbers of devices, pipes, and other members installed outside the reaction tank can be minimized, the equipment and labor required to prevent liquid leakage due to high pressure can be minimized.) Further, by minimizing the distance from the micro-nano bubble generator to the point where the reactant-containing liquid containing the micro-bubbles is supplied, it is possible to prevent the efficiency from being lowered due to the coalescence of the micro-nano bubbles in the piping.

In addition, the gas-liquid reaction device of the present invention and the gas-liquid reaction method using this gas-liquid reaction device have the following excellent effects by having the above-mentioned second feature.
〇 The liquid phase reactant-containing liquid can be agitated more efficiently and economically.
〇 Number of micro-nano bubbles Adjust the average diameter and total number of bubbles not only by the pressure and flow rate of the reactant-containing liquid supplied to the micro-nano bubble generator, but also by the pressure of the reaction gas existing in the gas phase of the reaction vessel. Can be done.

1 Reaction tank 2 Liquid supply device 3 Pressurized gas supply device 4 Micro-nano bubble generator 5 Pump (provided outside the reaction tank) 6 Internal pump (provided inside the reaction tank) 7 Reaction tank stirrer 8 Reaction gas Piping for guiding and supplying a reactant-containing liquid containing micro-nano bubbles to the inside of the liquid phase A Liquid containing a reactant (reactant-containing liquid)
B Gas containing reactive gas (reactive gas)
C Liquid phase of the reaction vessel D Gas phase of the reaction vessel E Liquid containing the reactants present in the liquid phase of the reaction vessel F Reaction gas existing in the gas phase of the reaction vessel G Liquid containing the reactants containing micro-nanobubbles of the reaction gas 11 Inlet 12 Throat 13 Suction 14 Gas inlet 15 Outlet 105 Pump 110 Reactor 140 High shearing device 207 Filter 208 Aromatic nitro compound solution 209 Vial bottle

Claims (14)

An airtightly sealed reaction vessel, a liquid supply device that supplies a liquid containing a reactant to the reaction vessel, and a pressurized gas supply device that supplies a gas containing a pressurized reaction gas to the reaction vessel. It is a gas-liquid reactor equipped with
A micro-nano bubble generator is provided in the reaction vessel separately from the inner wall surface of the reaction vessel.
Only the liquid existing in the liquid phase of the reaction tank and the gas existing in the gas phase of the reaction tank are supplied to the micro-nano bubble generator, and the micro-nano bubble generator brings the liquid phase of the reaction tank into the liquid phase. A gas-liquid reactor characterized by generating micro-nano bubbles of the gas. The gas-liquid reactor according to claim 1, wherein the liquid containing the gas micro-nano bubbles is supplied from the micro-nano bubble generator to the liquid phase of the reaction vessel. The gas-liquid reactor according to claim 1 or 2, wherein the micro-nano bubble generator is of a type driven by using a liquid flow. The liquid existing in the liquid phase of the reaction tank is pressurized and supplied to the micro-nano bubble generator, and the gas is sucked from the gas phase of the reaction tank by the negative pressure generated thereby to create micro-nano bubbles in the liquid. The gas-liquid reactor according to any one of claims 1 to 3, wherein the gas-liquid reactor is contained. The gas-liquid reactor according to any one of claims 1 to 4, wherein the micro-nano bubble generator is provided in the gas phase of the reaction vessel. The gas-liquid reactor according to any one of claims 1 to 4, wherein the micro-nano bubble generator is provided in the liquid phase of the reaction vessel. The gas-liquid reactor according to any one of claims 1 to 4, wherein the micro-nano bubble generator is provided across the gas phase and the liquid phase of the reaction tank. The gas-liquid reactor according to any one of claims 1 to 7, wherein a pump installed outside the reaction vessel is used as a means for pressurizing and supplying the liquid to the micro-nano bubble generator. The gas-liquid reactor according to any one of claims 1 to 7, wherein a pump installed inside the reaction vessel is used as a means for pressurizing and supplying the liquid to the micro-nano bubble generator. As a means for pressurizing and supplying the liquid to the micro-nano bubble generator, a pump impeller provided inside the reaction vessel is rotationally driven by applying an electromagnetic force, a magnetic force, or the like from the outside of the reaction vessel. , The gas-liquid reactor according to any one of claims 1 to 7. One of claims 1 to 10, wherein the pressurized gas supply device includes a supply control device that controls a supply amount of the gas according to the pressure of the gas in the gas phase of the reaction tank. The gas-liquid reactor according to. The gas-liquid according to any one of claims 1 to 11, further comprising a discharge device for discharging the liquid in the liquid phase of the reaction tank while keeping the reaction tank in an airtightly sealed state. Reactor. The gas-liquid reaction device according to claim 12, wherein the discharge device includes a discharge control device that controls the discharge amount of the liquid according to the liquid level of the liquid phase of the reaction tank. A gas-liquid reaction method comprising reacting a liquid containing a reactant with a reaction gas by the gas-liquid reactor according to any one of claims 1 to 13.

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